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Properties and Characteristics of Graphite SPECIALTY MATERIALS PROPERTIES AND CHARACTERISTICS OF GRAPHITE For the semiconductor industry May 2013 INTRODUCTION Introduction Table of Contents As Entegris has continued to grow its market share of Introduction .............................................................1 manufactured graphite material and to expand their usage into increasingly complex areas, the need to Structure ..................................................................2 be more technically versed in both Entegris’ POCO® graphite and other manufactured graphite properties Apparent Density .....................................................6 and how they are tested has also grown. It is with this Porosity ....................................................................8 thought in mind that this primer on properties and characteristics of graphite was developed. Hardness ................................................................11 POCO, now owned by Entegris, has been a supplier Compressive Strength .............................................12 to the semiconductor industry for more than 35 years. Products include APCVD wafer carriers, E-Beam cruci- Flexural Strength ...................................................14 bles, heaters (small and large), ion implanter parts, Tensile Strength .....................................................16 LTO injector tubes, MOCVD susceptors, PECVD wafer trays and disk boats, plasma etch electrodes, quartz Modulus of Elasticity .............................................18 replacement parts, sealing plates, bonding fixtures and sputtering targets. Entegris has a wide range of Electrical Resistivity ..............................................19 materials, as well as post-processing and machining Thermal Expansion ................................................21 capabilities to meet the demanding requirements of semiconductor processing. Thermal Conductivity .............................................22 With an accumulation of experience and data in Thermal Shock .......................................................24 testing POCO graphites as well as other manufactured graphites, it is now possible to describe the properties Specific Heat ..........................................................26 and testing techniques and their interrelationship. Emissivity ...............................................................28 The very discussion of these issues will bring forth many of the reasons why POCO graphites with their Ash ..........................................................................30 unique properties are superior to other manufactured graphites. Oxidation ................................................................32 The purpose of this primer is to introduce the reader Appendix A .............................................................34 to graphite properties and to describe testing tech- Appendix B .............................................................35 niques, which enable true comparisons between a multitude of manufactured graphites. POCO graphites Appendix C Bibliography .......................................36 come in many grades, each designed for a specific range of applications. In the semiconductor industry, For More Information ............................................38 these are represented by grades such as SFG, CZR, Terms and Conditions of Sale ................................38 TRA, DFP, HPD, PLS, SCF and ZEE. These are the materials upon which POCO facility has built its Product Warranties ................................................38 reputation as a manufacturer of the best graphites in the world. ENTEGRIS, INC. PROPERTIES AND CHARACTERISTICS OF GRAPHITE 1 STRUCTURE Structure TABLE 1-1. PROPERTIES OF THE ELEMENT CARBON Name: Carbon Definition: Carbon, the Element Symbol: C Carbon is the sixth element on the periodic table and Atomic number: 6 can be found in abundance in the sun, stars, comets Atomic mass: 12.0107 amu and atmospheres of most planets. Melting point: 3500.0°C Carbon is a Group 14 element (on older periodic 3773.15 K tables, Group IVA) along with silicon, germanium, 6332.0°F tin and lead. Carbon is distributed very widely in Boiling point: 4827.0°C nature (Figure 1-1). 5100.15 K 8720.6°F Number of protons/electrons: 6 Atomic number 6 12.011 Atomic weight Number of neutrons: 6, 7, 8 Classification: Non-metal C Crystal structure: Hexagonal Carbon Cubic Crystal structure 4 Common oxidation state Density @ 293 K: Graphite – 2.26 g/cm3 Diamond – 3.53 g/cm3 Figure 1-1. Carbon as on the periodic table Color: Black, gray In 1961, the International Union of Pure and Applied The history of manufactured graphite began at the Chemistry (IUPAC) adopted the isotope 12C as the end of the 19th century with a surge in carbon manu- basis for atomic weights. Carbon-14, 14C, an isotope facturing technologies. The use of the electrical with a half-life of 5730 years, is used to date such resistance furnace to manufacture synthetic graphite materials as wood, archeological specimens, etc. led to the development of manufactured forms of car- Carbon-13, 13C, is particularly useful for isotopic label- bon in the early part of the 20th century and more ing studies since it is not radioactive, but has a spin recently, to a wide variety of high-performance materi- I = 1⁄2 nucleus and therefore a good NMR nucleus. als such as carbon fibers and nanotubes (Figure 1-2). Carbon has four electrons in its valence shell (outer Forms of Carbon shell). The electron configuration in carbon is 1s2 2s2 2p2. Since this energy shell can hold eight electrons, Carbon is found free in nature in three allotropic each carbon atom can share electrons with up to four forms: amorphous carbon, graphite and diamond. different atoms. This electronic configuration gives More recently, a fourth form of carbon, buckminster- carbon its unique set of properties (Table 1-1). Carbon fullerene, C60, has been discovered. This new form can combine with other elements as well as with itself. of carbon is the subject of great interest in research This allows carbon to form many different compounds laboratories today. Within the past few years, this of varying size and shape. research has centered on graphene and its derivatives, which have the potential to bring about a fundamental Carbon is present as carbon dioxide in the atmosphere change in the semiconductor/electronic industry. and dissolved in all natural waters. It is a component of rocks as carbonates of calcium (limestone), magne- Carbon alone forms the familiar substances graphite sium and iron. Coal, petroleum and natural gas are and diamond. Both are made only of carbon atoms. chiefly hydrocarbons. Carbon is unique among the ele- Graphite is very soft and slippery, while diamond is ments in the vast number of varieties of compounds it one of the hardest substances known to man. Carbon, can form. Organic chemistry is the study of carbon and as microscopic diamonds, is found in some meteorites. its compounds. Natural diamonds are found in ancient volcanic “pipes” such as found in South Africa. If both graphite and diamond are made only of carbon atoms, what gives them different properties? The answer lies in the way the carbon atoms form bonds with each other. 2 PROPERTIES AND CHARACTERISTICS OF GRAPHITE ENTEGRIS, INC. STRUCTURE Pre-1880 Lampblack (writing) Charcoals (gunpowder, medicine, deodorants) Natural graphite (writing material) 1880–1940 Activated carbons Carbon blacks 109° 1.54 Å Coal coking (coal-tar pitch) Delayed coking Synthetic graphite and diamond 1940-2013 3.58 Å Carbon fibers (PAN) Figure 1-3. The crystal structure of diamond Carbon fibers (pitch-based) The forces within and between crystallites deter- Carbon fibers (microporous) mine the extreme difference in properties between Carbon/resin composites these two forms. In diamond, the crystal structure is face-centered cubic (Figure 1-3). The interatomic Carbon/carbon composites distance is 1.54 Å with each atom covalently bonded Specialty activated carbons to four other carbons in the form of a tetrahedron. Carbon as a catayst support This interatomic distance is close to that found in aliphatic hydrocarbons, which is in distinction to Carbon whiskers/filaments the smaller 1.42 Å carbon-carbon distance found in Prosthetics graphite and aromatic hydrocarbons (1.39 Å in ben- Intercalation compounds zene). This three-dimensional isotropic structure accounts for the extreme hardness of diamond. Graphite/oxide refractories Pyrolytic carbon 700 Solid Glassy carbon III Mesocarbon microbeads 600 Diamond films Diamond-like films Elastic carbon 500 Diamond Fullerenes Nanotubes 400 Liquid Nanorods Graphene 300 Pressure (kiloatmospheres) 200 Diamond and Figure 1-2. Growth of carbon materials1 metastable graphite 100 Gr. Graphite and metastable diamond 0 01000 2000 3000 4000 5000 T, K 1 Adapted from Marsh, H. et al., Introduction to Carbon Technologies, (1997), pp. 4, 521. Figure 1-4. The carbon phase diagram ENTEGRIS, INC. PROPERTIES AND CHARACTERISTICS OF GRAPHITE 3 STRUCTURE Thermodynamically, graphite at atmospheric pressure a given plane also provides the electron bond network is the more stable form of carbon. Diamond is trans- responsible for the high mobility (electronic) of graph- formed to graphite above 1500°C (Figure 1-4). ite. This would appear more correct, since van der Waals forces are the result of dipole moments, which would not account for the high mobility. A Consequently, weak forces between layer planes account for (a) the
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